CN108396344A - With the electrolytic copper foil and preparation method thereof for distorting band-like unordered winding microstructure - Google Patents
With the electrolytic copper foil and preparation method thereof for distorting band-like unordered winding microstructure Download PDFInfo
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- CN108396344A CN108396344A CN201810226778.2A CN201810226778A CN108396344A CN 108396344 A CN108396344 A CN 108396344A CN 201810226778 A CN201810226778 A CN 201810226778A CN 108396344 A CN108396344 A CN 108396344A
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- Prior art keywords
- copper
- axis direction
- copper foil
- electrolytic copper
- band
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011889 copper foil Substances 0.000 title claims abstract description 29
- 238000004804 winding Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 55
- 238000009713 electroplating Methods 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000975 dye Substances 0.000 claims abstract description 7
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 125000001741 organic sulfur group Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 2
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- 238000005728 strengthening Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a kind of electrolytic copper foils and preparation method thereof for having and distorting band-like unordered winding microstructure, the crystal grain of the electrolytic copper foil, which shows to have, significantly distorts band-like unordered winding arrangement, there is long axis direction and short-axis direction, and its long axis direction and short-axis direction all have a degree of distortion；The electrolytic copper foil is prepared by direct current electrode position technique, required electroplating solution includes base soln and electroplating additive, wherein base soln is copper sulphate, sulfuric acid and trace chlorine, and electroplating additive selects novel sour copper accelerator, novel sour copper deactivator and the novel sour copper leveling agent of non-dyestuff.The present invention creatively utilizes novel electroplating additive, and the electrolytic copper foil for having in crystal grain and distorting band-like unordered winding microstructure is successfully prepared using the method for direct current electrode position, it reduces and prepares difficulty and production cost, improve production efficiency, the layers of copper material being electroplated out has good mechanical property, has stronger tensile strength and ductility.
Description
Technical field
The present invention relates to a kind of electrolytic copper foils, and in particular to a kind of crystal grain has the microstructure of the band-like unordered winding of distortion
And realize the material preparation method of the microstructure.
Background technology
Common copper product usually its mechanical property is poor, especially cathode copper material system, such as with Young's modulus
It is smaller, the shortcomings of ductility is poor, so the mechanical characteristic for improving electrolytic copper foil is also one of active demand of industrial quarters.At present
The method that mainstream improves material mechanical performance, mostly uses various strengthening mechanisms, such as solution strengthening, dispersion-strengtherning, precipitation strength,
But these means not can be used substantially in electro-coppering field.Electrolytic copper foil mostly uses the means such as refined crystalline strengthening, texture strengthening, still
The opposite usual ductility of refined crystalline strengthening is difficult raising, it is difficult to more than 3%, and texture strengthening is then the top-priority side of electrolytic copper foil
Method.Mostly it is at present to allow crystal grain that there is preferred orientation in some direction using texture strengthening, so material mechanical performance will present one
The characteristics of fixed anisotropy.There is good isotropism in the field of certain particular/special requirements, such as material mechanical performance, and
Common texture strengthening is because have very strong anisotropy to there is limitation in application field.
Theoretically, if can have a kind of and copper product for mutually tangling unordered with crystal grain, due to this special
Microstructure, copper crystal orientation of particles show as it is unordered, performance be isotropism.But with the band-like unordered of distortion
The current industry of microstructure of winding is very rare, especially the electrolytic copper foil market of the microstructure with band-like unordered winding
It is upper not yet visible.Current relatively feasible method is to select electro-plating method to be prepared, but the common plating in common market adds
Add agent usually helpless, yet there are no relevant research report.
Invention content
In view of the drawbacks of the prior art, the present invention is intended to provide a kind of having the electricity for distorting band-like unordered winding microstructure
Copper foil and preparation method thereof is solved, can be prepared under higher current density with the special microcosmic knot for distorting band-like unordered winding
The copper crystal grain of structure.
To realize above-mentioned technical purpose and the technique effect, the invention is realized by the following technical scheme：
The a kind of of the present invention has the electrolytic copper foil for distorting band-like unordered winding microstructure, in its microstructure, crystal grain
With significantly distorting band-like unordered winding arrangement, like a ball of string for mixed and disorderly unordered and intensive winding, that is, have long axis direction and
Short-axis direction, and all there is a degree of distortion in its long axis direction and short-axis direction.
Further, the long axis direction size of the crystal grain is 20nm-3 μm, and the short-axis direction size of the crystal grain is
10nm-1μm。
A kind of preparation method with the electrolytic copper foil for distorting band-like unordered winding microstructure of the present invention, including it is following
Step：
Step 1）Select copper product as electroplated sample；
Step 2）A certain amount of copper sulphate and sulfuric acid are weighed, and micro hydrochloric acid is added or sodium chloride is mixed and stirred for, makes its mixing
Uniformly, it is configured to the base soln of copper sulphate-sulfuric acid system；
Step 3）A certain amount of novel sour copper accelerator, novel sour copper deactivator and the novel sour copper leveling of non-dye-type are weighed respectively
Agent is configured to the electroplating additive of the novel copper plating additive system of non-dyestuff after being mixed with water；
Step 4）Electroplating additive obtained is mixed with base soln, is configured to the electroplating solution of acid copper-plating system；
Step 5）Using direct current electrode position technique, electroplated sample is electroplated under certain current density to get.
Further, in the base soln, a concentration of 40-60g/L of the bivalent cupric ion, the concentration of the sulfuric acid
For 90-140g/L, the ion concentration is 40-60ppm.
Further, the hydrochloric acid in the copper sulphate and the sulfuric acid solution in the copper-bath is extra-pure grade.
Further, the main component of the novel sour copper accelerator is organic sulfur sulfonate, in the electroplating solution
A concentration of 3-5mL/L；The main component of the novel sour copper deactivator is polyethylene glycol, the concentration in the electroplating solution
For 5-15mL/L；The main component of the novel sour copper leveling agent of the non-dyestuff is the novel quaternary ammonium that a kind of the applicant formerly invents
Salt（" a kind of application of acid copper leveling agent ", patent No. ZL201310731443.3）, a concentration of 30- in the electroplating solution
80mL/L。
Further, step 5）In, the ranging from 2-30A/dm of current density2。
Further, step 5）In, the time of plating is 4-7.5min.
It is worth noting that, the preparation method of the present invention is suitable for copper product, but it is not limited to copper product.
The beneficial effects of the invention are as follows：
The present invention by using copper sulphate-sulfuric acid system as copper-plated base soln, using the copper plating additive of independent research,
Using common direct current electrode position technique, crystal grain in coating is prepared and the electricity for having and distorting band-like unordered winding microstructure is presented
Solve copper foil.
Compared with the existing technology, copper coating of the invention using common electroplating technology, greatly reduces realization first
Crystal grain has the difficulty for distorting band-like unordered winding microstructure, and cost has been significantly reduced in production；Secondly, the copper being electroplated out
Layer material has good mechanical property, has stronger tensile strength and ductility；Finally, added using the copper facing of independent research
Add agent, which can carry higher current density, to realize high speed electrodeposition, so significantly improving production efficiency.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention and attached drawing is coordinated to be described in detail below.This hair
Bright specific implementation mode is shown in detail by following embodiment and its attached drawing.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and is constituted part of this application, this hair
Bright illustrative embodiments and their description are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 is the XRD of the copper coating in first embodiment of the invention（X-ray diffractometer）Collection of illustrative plates.
Fig. 2 is the copper coating cross-section morphology figure in first embodiment of the invention, wherein Fig. 2（a）With（b）Respectively
40K times and 20K times lower copper coating microscopic appearance figure.
Fig. 3 is the XRD of the copper coating in second embodiment of the invention（X-ray diffractometer）Collection of illustrative plates.
Fig. 4 is the copper coating cross-section morphology figure in second embodiment of the invention, wherein Fig. 4（a）With（b）Respectively
40K times and 20K times lower copper coating microscopic appearance figure.
Specific implementation mode
It is below with reference to the accompanying drawings and in conjunction with the embodiments, next that the present invention will be described in detail.
Embodiment 1
A kind of to have the electrolytic copper foil for distorting band-like unordered winding microstructure, in its microstructure, crystal grain has apparent
The band-like unordered winding arrangement of distortion like a ball of string for mixed and disorderly unordered and intensive winding there is long axis direction and short-axis direction,
And all there is a degree of distortion in its long axis direction and short-axis direction, the long axis direction size of the crystal grain is 20nm-3 μm,
The short-axis direction size of the crystal grain is 10nm-1 μm.
A kind of preparation method with the electrolytic copper foil for distorting band-like unordered winding microstructure, is as follows：
By the copper-bath of a concentration of 50g/L of bivalent cupric ion, sulfuric acid concentration is that 100g/L sulfuric acid solutions and chlorion are dense
Degree is the mixed in hydrochloric acid of 50ppm and stirs two hours, so that it is uniformly mixed, is configured to base soln.
Select novel sour copper accelerator（Main component is organic sulfur sulfonate）, novel sour copper deactivator（Main component is
Polyethylene glycol）With the novel sour copper leveling agent of non-dye-type（A kind of novel quaternary ammonium salt that the applicant had previously applied, patent name：
A kind of application of non-dyestuff system leveling agent, the patent No.：ZL201310731859.5）These three additives are as electroplating additive.
A concentration of 3mL/L of the wherein novel sour copper accelerator in entire electroplating solution, novel acid copper deactivator is in entire electroplating solution
In a concentration of 12mL/L, a concentration of 40mL/L of the novel sour copper leveling agent of non-dye-type in entire electroplating solution.
Above-mentioned three kinds of electroplating additives are mixed with base soln, are configured to electroplating solution.Sample with plating is existed
10A/dm2Current density under, be electroplated 7.5min.It is shown in Figure 1 after plating, electroplated sample is surveyed using X-ray diffractometer
Determine high preferred orientation, Fig. 1 shows the XRD of the sample copper coating in the present embodiment（X-ray diffractometer）Collection of illustrative plates.It is shown in Figure 2, then
Utilize SEM（Electron microscope）To sample making sectional slice view, Fig. 2 indicates that the sample copper coating section in the present embodiment is microcosmic
Shape appearance figure, wherein scheming（a）With（b）Respectively 40K times and 20K times lower copper coating microscopic appearance.From the figures it is clear that
The state of the band-like unordered winding with distortion is presented in the electrolytic copper foil that the present embodiment is prepared, crystal grain.
Embodiment 2
A kind of to have the electrolytic copper foil for distorting band-like unordered winding microstructure, in its microstructure, crystal grain has apparent
The band-like unordered winding arrangement of distortion like a ball of string for mixed and disorderly unordered and intensive winding there is long axis direction and short-axis direction,
And all there is a degree of distortion in its long axis direction and short-axis direction, the long axis direction size of the crystal grain is 20nm-3 μm,
The short-axis direction size of the crystal grain is 10nm-1 μm.
A kind of preparation method with the electrolytic copper foil for distorting band-like unordered winding microstructure, is as follows：
By the copper-bath of a concentration of 40g/L of bivalent cupric ion, sulfuric acid concentration is that 120g/L sulfuric acid solutions and chlorion are dense
Degree is the mixed in hydrochloric acid of 50ppm and stirs three hours, so that it is uniformly mixed, is configured to base soln.
Select novel sour copper accelerator（Main component is organic sulfur sulfonate）, novel sour copper deactivator（Main component is
Polyethylene glycol）With the novel sour copper leveling agent of non-dye-type（A kind of novel quaternary ammonium salt that the applicant had previously applied, patent name：
A kind of application of non-dyestuff system leveling agent, the patent No.：ZL201310731859.5）These three additives are as electroplating additive.
A concentration of 4mL/L of the wherein novel sour copper accelerator in entire electroplating solution, novel acid copper deactivator is in entire electroplating solution
In a concentration of 10mL/L, a concentration of 70mL/L of the novel sour copper leveling agent of non-dye-type in entire electroplating solution.
Above-mentioned three kinds of electroplating additives are mixed with base soln, are configured to electroplating solution.By the sample with plating in 8A/
dm2Current density under, be electroplated 4min.It is shown in Figure 3 after plating, crystal face is measured to electroplated sample using X-ray diffractometer
It is orientated, Fig. 3 indicates the XRD of the sample copper coating in the present embodiment（X-ray diffractometer）Collection of illustrative plates.It is shown in Figure 4, it recycles
SEM（Electron microscope）To sample making sectional slice view, Fig. 4 indicates the sample copper coating cross-section morphology in the present embodiment
Figure, wherein Fig. 4（a）With（b）Respectively 40K times and 20K times lower copper coating microscopic appearance.From the figures it is clear that this
The state of the band-like unordered winding with distortion is equally presented in the electrolytic copper foil that embodiment is prepared, crystal grain.
Above-described embodiment simply to illustrate that the present invention technical concepts and features, it is in the art the purpose is to be to allow
Those of ordinary skill cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all
It is the equivalent changes or modifications made by the essence according to the content of present invention, should all covers within the scope of the present invention.
Claims (8)
1. a kind of having the electrolytic copper foil for distorting band-like unordered winding microstructure, it is characterised in that：In its microstructure,
Crystal grain, which has, significantly distorts band-like unordered winding arrangement, that is, has long axis direction and short-axis direction, and its long axis direction and short
All there is a degree of distortion in axis direction.
2. according to claim 1 have the electrolytic copper foil for distorting band-like unordered winding microstructure, it is characterised in that：Institute
The long axis direction size for stating crystal grain is 20nm-3 μm, and the short-axis direction size of the crystal grain is 10nm-1 μm.
3. a kind of preparation method of electrolytic copper foil as claimed in claim 1 or 2, which is characterized in that include the following steps：
Step 1）Select copper product as electroplated sample；
Step 2）A certain amount of copper sulphate and sulfuric acid are weighed, and micro hydrochloric acid is added or sodium chloride is mixed and stirred for, makes its mixing
Uniformly, it is configured to the base soln of copper sulphate-sulfuric acid system；
Step 3）A certain amount of novel sour copper accelerator, novel sour copper deactivator and the novel sour copper leveling of non-dye-type are weighed respectively
Agent is configured to the electroplating additive of the novel copper plating additive system of non-dyestuff after being mixed with water；
Step 4）Electroplating additive obtained is mixed with base soln, is configured to the electroplating solution of acid copper-plating system；
Step 5）Using direct current electrode position technique, electroplated sample is electroplated under certain current density to get.
4. the preparation method of electrolytic copper foil according to claim 3, it is characterised in that：In the base soln, described two
A concentration of 40-60g/L of valence copper ion, a concentration of 90-140g/L of the sulfuric acid, the ion concentration are 40-60ppm.
5. the preparation method of electrolytic copper foil according to claim 3, it is characterised in that：Sulfuric acid in the copper-bath
Hydrochloric acid in copper and the sulfuric acid solution is extra-pure grade.
6. the preparation method of electrolytic copper foil according to claim 3, it is characterised in that：The novel sour copper accelerator at
It is divided into organic sulfur sulfonate, a concentration of 3-5mL/L in the electroplating solution；The ingredient of the novel sour copper deactivator is poly-
Ethylene glycol, a concentration of 5-15mL/L in the electroplating solution；The ingredient of the novel sour copper leveling agent of the non-dyestuff is one kind
Quaternary ammonium salt, a concentration of 30-80mL/L in the electroplating solution.
7. the preparation method of electrolytic copper foil according to claim 3, it is characterised in that：Step 5）In, the model of current density
It encloses for 2-30A/dm2。
8. the preparation method of electrolytic copper foil according to claim 3, it is characterised in that：Step 5）In, the time of plating is
4-7.5min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226778.2A CN108396344B (en) | 2018-03-19 | 2018-03-19 | Electrolytic copper foil with distorted banded disordered winding microstructure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226778.2A CN108396344B (en) | 2018-03-19 | 2018-03-19 | Electrolytic copper foil with distorted banded disordered winding microstructure and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108396344A true CN108396344A (en) | 2018-08-14 |
| CN108396344B CN108396344B (en) | 2021-02-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112580A (en) * | 2018-09-18 | 2019-01-01 | 苏州昕皓新材料科技有限公司 | One kind having anisotropic metal material of thermodynamics and preparation method thereof |
| WO2023151029A1 (en) * | 2022-02-11 | 2023-08-17 | Suzhou Shinhao Materials Llc | Method for electroplating nanograined copper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924269A (en) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | Application of non-pigmentary leveling agent |
| CN103924268A (en) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | Application of acid copper leveling agent |
| CN106521573A (en) * | 2016-11-23 | 2017-03-22 | 苏州昕皓新材料科技有限公司 | Method for producing electroplated copper layer with preferential orientation growth structure, and application thereof |
| CN106757191A (en) * | 2016-11-23 | 2017-05-31 | 苏州昕皓新材料科技有限公司 | A kind of copper crystal particle with preferred orientation high and preparation method thereof |
-
2018
- 2018-03-19 CN CN201810226778.2A patent/CN108396344B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924269A (en) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | Application of non-pigmentary leveling agent |
| CN103924268A (en) * | 2013-12-26 | 2014-07-16 | 苏州昕皓新材料科技有限公司 | Application of acid copper leveling agent |
| CN106521573A (en) * | 2016-11-23 | 2017-03-22 | 苏州昕皓新材料科技有限公司 | Method for producing electroplated copper layer with preferential orientation growth structure, and application thereof |
| CN106757191A (en) * | 2016-11-23 | 2017-05-31 | 苏州昕皓新材料科技有限公司 | A kind of copper crystal particle with preferred orientation high and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109112580A (en) * | 2018-09-18 | 2019-01-01 | 苏州昕皓新材料科技有限公司 | One kind having anisotropic metal material of thermodynamics and preparation method thereof |
| WO2020057060A1 (en) * | 2018-09-18 | 2020-03-26 | Suzhou Shinhao Materials Llc | A metal material with thermodynamic anisotropy and a method of preparing the same |
| US11242607B2 (en) | 2018-09-18 | 2022-02-08 | Suzhou Shinhao Materials Llc | Metal material with thermodynamic anisotropy and a method of preparing the same |
| US11802345B2 (en) | 2018-09-18 | 2023-10-31 | Suzhou Shinhao Materials Llc | Metal material with thermodynamic anisotropy and a method of preparing the same |
| WO2023151029A1 (en) * | 2022-02-11 | 2023-08-17 | Suzhou Shinhao Materials Llc | Method for electroplating nanograined copper |
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| Publication number | Publication date |
|---|---|
| CN108396344B (en) | 2021-02-12 |
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